CN116655610A - Volatile amine fluorescent probe and application of dual-channel indicating card prepared by same in fish freshness detection - Google Patents
Volatile amine fluorescent probe and application of dual-channel indicating card prepared by same in fish freshness detection Download PDFInfo
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- 241000251468 Actinopterygii Species 0.000 title claims abstract description 80
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 58
- 150000001412 amines Chemical class 0.000 title claims abstract description 31
- 238000001514 detection method Methods 0.000 title claims abstract description 17
- 239000000523 sample Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 230000009977 dual effect Effects 0.000 claims abstract description 5
- 235000013372 meat Nutrition 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 14
- 230000008859 change Effects 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000012544 monitoring process Methods 0.000 claims description 7
- 150000001562 benzopyrans Chemical class 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 238000011897 real-time detection Methods 0.000 abstract description 2
- 235000019688 fish Nutrition 0.000 description 60
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 description 42
- 229940063675 spermine Drugs 0.000 description 21
- 241000972773 Aulopiformes Species 0.000 description 19
- 235000019515 salmon Nutrition 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- -1 amine compounds Chemical class 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 8
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
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- 239000000126 substance Substances 0.000 description 3
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- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000002503 metabolic effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
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- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
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- APJYDQYYACXCRM-UHFFFAOYSA-N tryptamine Chemical compound C1=CC=C2C(CCN)=CNC2=C1 APJYDQYYACXCRM-UHFFFAOYSA-N 0.000 description 2
- DZGWFCGJZKJUFP-UHFFFAOYSA-N tyramine Chemical compound NCCC1=CC=C(O)C=C1 DZGWFCGJZKJUFP-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005700 Putrescine Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
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- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 235000005911 diet Nutrition 0.000 description 1
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- 235000013332 fish product Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 229920006255 plastic film Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 229960003732 tyramine Drugs 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
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- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
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Abstract
The utility model provides a volatile amine fluorescent probe and binary channels instruction card's that preparation is in flesh of fish freshness detection application, fluorescent probe structural formula is as follows:the fish flesh freshness double-channel indicator card prepared by the fluorescent probe takes a fish shape as a main body, and consists of six square colorimetric cards with the same area and a circular sensing label, wherein the upper half area of the colorimetric card is sequentially provided with fresh, qualified and spoiled natural light colorimetric areas from left to right, and the lower half area of the colorimetric card is sequentially provided with fresh, qualified and spoiled ultraviolet light colorimetric areas from left to right. The advantages are that: the probeThe colorimetric and fluorescent dual-response can be carried out on various volatile amines in an aqueous system, and the sensitivity is high; the probe is prepared into a sensing label, can be used for nondestructive rapid real-time detection of fish freshness, and has accurate and reliable results.
Description
Technical Field
The invention relates to a volatile amine fluorescent probe and application of a dual-channel indicating card prepared by the same in fish freshness detection.
Background
As people pay more attention to diet health, consumers mostly select foods with high safety, health and nutritive value, and fishes just can meet the demands of masses, so that the sales of the fish products in China is greatly increased. However, the freshness of the fish meat can directly affect the quality of the fish meat, and the deteriorated fish meat not only causes huge economic loss but also has harmful effects on the health of human bodies, so that how to conveniently and quickly evaluate the quality and freshness of the fish meat with low cost becomes an increasingly important problem. At present, deep sea fish are sold in plastic sealing bags or vacuum packages in a split manner so as to ensure the quality of the fish, but the traditional method for detecting the freshness of the fish mostly needs to damage the outer package of the product, takes time for pretreatment and is complex and cumbersome in detection method. In recent years, although many analysis methods have been developed for detecting the freshness of fish meat, expensive instruments are generally required, the freshness of fish meat cannot be displayed in real time, and the requirements of naked eyes identification of retailers or consumers cannot be met. The development of the method for evaluating the freshness of the fish meat, which does not damage the outer package of the product, has low cost, simple operation and accurate and reliable detection, is still the key content of attention of vast researchers.
In recent years, intelligent packaging has shown good application prospects in monitoring fish meat quality, and chemical or biological indicators, time-temperature indicators and the like are used for intelligent packaging design. In these various methods, monitoring of fish freshness by designing intelligent packages to analyze volatile metabolites produced by spoilage of fish meat has been widely reported, but partial freshness indication packages are affected by poor hygroscopicity of the carrier or limited by the humid environment within the package, directly affecting the sensitivity and effectiveness of the sensor tag. 37-42 as in documents Food science and biotechnology, 2017, 26 (1); carbohydrate Polymers 255 (2021) 117488 has a sensor tag for monitoring freshness of fish meat by pH sensitivity, but color change by colorimetric recognition is not clear enough, and a discrimination error is liable to occur at the time of application. Therefore, a colorimetric and fluorescent dual-response sensing tag is developed, and the freshness level of the fish meat is comprehensively judged through double-channel color development, so that erroneous judgment can be reduced. In addition, near infrared fluorescent probes which are sensitive to the response of volatile amine, high in speed and capable of emitting light with the wavelength ranging from 600nm to 800 nm are developed, the probes are little interfered by background fluorescence, the fluorescence change is more obvious, and the application prospect is better.
Disclosure of Invention
The invention aims to solve the technical problem of providing a volatile amine fluorescent probe and application of a prepared dual-channel indicator card in fish freshness detection. The probe can be used in DMF/H 2 The O=1:1 (v/v) system has colorimetric and fluorescent dual response to various amine compounds, high sensitivity, quick response time and near infrared emission; the probe is prepared into a sensing label, so that qualitative analysis of the freshness of the fish in the packaging box can be realized, a sample and complex pretreatment are not required to be destroyed, the result is accurate and reliable, and the method can be used for nondestructive rapid real-time detection of the freshness of the fish.
The utility model provides a volatile amine fluorescent probe and binary channels instruction card's that preparation is in flesh of fish freshness detection application, this fluorescent probe structural formula is as follows:
further, the specific synthesis steps of the fluorescent probe are as follows:
ethanol is taken as a solvent, benzopyran derivatives and 2-thiobarbituric acid are added according to the mol ratio of 1 (1-1.5), and the benzopyran derivatives are 6- (diethylamino) -1,2-Dihydrocyclopentane [ b ]]Benzopyran-3-carboxaldehydeThen adding piperidine according to the mass ratio of benzopyran derivative to piperidine of 100:1, heating, refluxing and stirring for 2-4 hours, cooling to room temperature, filtering and collecting solid, washing with ethanol for 3 times to obtain fluorescent probe DCA-Tba。
The fish freshness double-channel indicator card prepared by the fluorescent probe is characterized in that the indicator card takes a fish shape as a main body, and consists of six square color cards with the same area and a circular sensing label, wherein the six squares are respectively a fresh color card, a qualified color card and a spoilage color card, and the indicator card is characterized in that: the color chart is divided into a natural light color comparison area and an ultraviolet light color comparison area, wherein the upper half area of the color chart is respectively a fresh natural light color comparison area, a qualified natural light color comparison area and a spoilage natural light color comparison area, and the lower half area of the color chart is respectively a fresh ultraviolet light color comparison area, a qualified ultraviolet light color comparison area and a spoilage ultraviolet light color comparison area.
The specific preparation process of the sensing label comprises the following steps:
3.95 mg fluorescent probe DCA-Tba is weighed and dissolved in 10 mL DMSO, round filter paper with the diameter of 2cm is placed in the solution to be soaked for 24 hours, and then the solution is taken out and dried, so that a fluorescent probe-loaded sensing label is obtained, and the sensing label is green when observed with naked eyes and shows no fluorescence under ultraviolet light.
Further, the color phase corresponding to the natural light ratio color zone of the fresh product is green, and the color phase corresponding to the ultraviolet light color comparison area of the fresh product is non-fluorescent; the hue corresponding to the natural light colorimetric region of the qualified product is light pink, and the hue corresponding to the ultraviolet colorimetric region of the qualified product is orange fluorescence; the color phase corresponding to the natural light color comparison area of the unqualified product is dark pink, and the color phase corresponding to the ultraviolet light color comparison area of the unqualified product is orange fluorescence.
An application of a fish freshness double-channel indicating card in judging fish freshness.
The utility model provides an application of flesh of fish freshness binary channels instruction card in judging flesh of fish freshness, places instruction card and flesh of fish sample in the packing carton, and sensing label does not contact with food direct contact, compares according to sensing label colour variation and standard color card, carries out real-time supervision to flesh of fish freshness, evaluates flesh of fish and locates the freshness grade.
Under visible light, the color of the sensing label is green, which indicates freshness, the color of the sensing label is light pink, which indicates qualification, and the color of the sensing label is dark pink, which indicates disqualification; under 365nm ultraviolet light irradiation, the color of the sensing label is fresh when the color of the sensing label is non-fluorescent, the color of the sensing label is orange fluorescent, the sensing label is qualified when the color of the sensing label is orange fluorescent, and the sensing label is unqualified when the color of the sensing label is orange fluorescent.
The invention has the beneficial effects that:
(1) The fluorescent probe has the characteristics of near infrared emission, the maximum emission wavelength can reach 720 nm, the interference of scattering and fluorescent background is small, the quantum efficiency is high, the fluorescent signal is stable, and the fluorescent probe can be used in DMF (dimethyl formamide)/H 2 O=1:1 (v/v) system species respond to a variety of amine compounds.
(2) The sensing label prepared by the fluorescent probe can detect the freshness of fish meat through colorimetric and fluorescent double channels, and the sensing label is matched with a standard colorimetric card, so that the freshness of the fish meat can be monitored in real time.
In conclusion, the fluorescent probe designed and synthesized by the invention not only can detect various amine compounds, but also can be prepared into a sensing label for identifying various volatile amines, the preparation process of the sensing label is simple, the fish freshness can be detected through colorimetric and fluorescent double channels, and the qualitative analysis is more accurate and reliable. The sensing tag can be used for monitoring the freshness of the fish in real time in a non-contact and non-destructive manner, can provide effective freshness information for manufacturers, retailers and consumers in time, and has good practical application value.
Drawings
FIG. 1 is a fluorescent probe DCA-Tba of the present invention 1 H NMR spectrum;
FIG. 2 is a fluorescent probe DCA-Tba of the present invention 13 C NMR spectrum;
FIG. 3 is a high resolution mass spectrum of the fluorescent probe DCA-Tba of the present invention;
FIG. 4 is a graph showing fluorescence emission spectra of the fluorescent probe DCA-Tba of the present invention before and after interaction with an amine compound;
FIG. 5 is a graph showing ultraviolet absorption spectra before and after the fluorescent probe DCA-Tba of the present invention reacts with amine compounds;
FIG. 6 is a fluorescence emission spectrum of the fluorescent probe DCA-Tba of the present invention after interaction with various concentrations of spermine;
FIG. 7 is an ultraviolet absorbance spectrum of the fluorescent probe DCA-Tba of the present invention before and after interaction with various concentrations of spermine;
FIG. 8 is a linear relationship between DCA-Tba fluorescence intensity and spermine concentration of the fluorescent probe of the present invention;
FIG. 9 is a linear relationship between the absorbance intensity of the fluorescent probe DCA-Tba of the invention and the concentration of spermine;
FIG. 10 is a graph showing the change in fluorescence intensity of the fluorescent probe DCA-Tba of the present invention at various pH values before and after the addition of spermine;
FIG. 11 is a graph showing the change of fluorescence intensity with time at 600nm after adding spermine to the fluorescent probe DCA-Tba of the present invention;
FIG. 12 is a photograph of a sensor tag prepared according to the present invention identifying changes in solar color (up) and changes in fluorescent color (down) before and after a volatile amine;
FIG. 13 is a photograph showing TVB-N content of salmon flesh and color of corresponding sensor tag under natural light and ultraviolet light irradiation at 4deg.C with prolonged storage time;
FIG. 14 is a standard color chart made according to the correspondence between TVB-N value of fish meat and color of the sensing tag; the upper layer of the standard colorimetric card is a fresh natural light colorimetric area, a qualified natural light colorimetric area and a spoilage natural light colorimetric area respectively from left to right, and the lower layer of the standard colorimetric card is a fresh ultraviolet light colorimetric area, a qualified ultraviolet light colorimetric area and a spoilage ultraviolet light colorimetric area respectively from left to right;
FIG. 15 is a graph showing the freshness of salmon flesh as determined by the combination of solar and ultraviolet color changes of the label and standard colorimetric card, when the sensor label prepared according to the present invention is stored at 4deg.C with salmon flesh; 4. the fish meat belongs to fresh products when stored at the temperature of 0 th day, and belongs to qualified products when stored at the temperature of 4 th day, and belongs to unqualified products when stored at the temperature of 8 th day;
FIG. 16 is a standard colorimetric card integrated with a sensor tag to produce an integrated tag that can rapidly colorimetrically and fluorescently determine the freshness of fish meat;
FIG. 17 is a graph showing the rapid determination of salmon flesh freshness by sunlight and ultraviolet light color, using the integrated tag prepared according to the present invention stored with salmon samples at room temperature of 25 ℃; the fish meat stored at room temperature 0 h was of fresh grade (top), when the fish meat stored at 18 th h was of acceptable grade (middle), when the fish meat stored at 32 th h was of unacceptable grade (bottom).
Detailed Description
The technical scheme of the invention is further described in detail below with reference to specific embodiments.
Example 1
The specific synthesis steps of the fluorescent probe DCA-Tba are as follows:
compounds DCA (538 mg,2 mmol) and 2-thiobarbituric acid (288 mg,2 mmol) in 10 mL ethanol were added followed by 5.4 mg piperidine to give a reaction mixture; the reaction mixture was heated under reflux and stirred for 2 hours, cooled to room temperature, and the crude product was collected by filtration as a greenish black solid, which was washed with ethanol to give fluorescent probe DCA-Tba having a yield of 85%; 1 h NMR spectrum, 13 The C NMR spectra and mass spectra are shown in FIGS. 1-3.
1 H NMR (400 MHz, DMSO-d 6 ) δ 11.65 (s, 2H), 8.15 (s, 1H), 7.59 (s, 1H), 7.46 (d, J = 9.0 Hz, 1H), 6.86 (d, J = 9.4 Hz, 1H), 6.81 (s, 1H), 3.50 (dd, J= 15.9, 8.9 Hz, 4H), 3.12 (s, 1H), 2.84 (s, 1H), 1.15 (t, J = 6.9 Hz, 3H), 1.05 (t, J = 7.0 Hz, 3H).
13 C NMR (101 MHz, DMSO-d 6 ) δ 176.81, 151.18, 139.57, 133.57, 131.96, 129.75, 118.91, 112.92, 111.80, 97.10, 55.14, 44.51, 28.74, 24.95, 18.79, 12.64.
HRMS (ESI - ) for C 21 H 21 N 3 O 3 S [M+H] + calcd: 396.1376, found: 396.1385。
Example 2
Compound DCA (13.467 g,50 mmol) dissolved in 50 mL ethanol and p-aminobenzoic acid (9.37 g,65 mmol) were added, then 135 mg piperidine was added, the reaction mixture was heated under reflux for 3 hours, cooled to room temperature, suction filtered, and the resulting crude product was collected and washed with ethanol to give fluorescent probe DCA-Tba in 77% yield; the fluorescent probe DCA-Tba of this example 1 The H NMR spectrum is shown in FIG. 1, 13 the C NMR spectrum is shown in FIG. 2, and the high resolution mass spectrum is shown in FIG. 3.
Example 3
The reaction mixture was heated under reflux with the addition of compound DCA (2.6934 g,10 mmol) and 2-thiobarbituric acid (2.16 g,15 mmol) dissolved in 20 mL ethanol followed by 27 mg piperidine, stirred for 4 hours, cooled to room temperature, and the resulting crude product was collected by filtration and washed with ethanol to give fluorescent probe DCA-Tba in 65% yield; the fluorescent probe DCA-Tba of this example 1 The H NMR spectrum is shown in FIG. 1, 13 the C NMR spectrum is shown in FIG. 2, and the high resolution mass spectrum is shown in FIG. 3.
1. Selectivity of fluorescent probe DCA-Tba for amine compounds
In 2mL DMF/H 2 The system of O=1:1 (v/v) was prepared by adding a fluorescent probe DCA-Tba solution to 10. Mu. Mol/L for later use, and 20. Mu.L of 50 mmol/L cyclohexanediamine, diethylamine, n-propylamine, isopropylamine, triethylamine, ethylamine, spermine, cadaverine, putrescine, 2-phenylethylamine, tyramine, tryptamine and aniline solutions were added respectively, and the fluorescence intensity changes were observed, as shown in FIG. 4, and the fluorescence intensity was enhanced in the vicinity of 600nm by the other 12 amine compound solutions except aniline, and the fluorescence was observed to change from non-fluorescent to pink or orange under irradiation of an ultraviolet lamp of 365 nm. The ultraviolet-visible spectrum of the test is shown in figure 5, after various amine compounds are added, the maximum absorption wavelength of other 12 amine compounds except aniline is obviously blue shifted, and the color change is obvious. The above results indicate that the fluorescent probe DCA-Tba is in DMF/H 2 O=1:1 (v/v) solublesThe liquid can realize colorimetric and fluorescent dual-channel identification on various amine compounds, and has excellent selectivity.
2. Identification performance of fluorescent probe DCA-Tba on representative amine compound spermine
First, DCA-Tba was tested for fluorescence and UV titration of amine compounds. Using spermine as an example, 10. Mu. Mol/L of fluorescent probe DCA-Tpa was tested in DMF/H 2 The relationship between the fluorescence intensity and the ultraviolet absorption intensity in O=1:1 (v/v) and the concentration of the spermine solution is shown in FIG. 6, when the concentration (0-40 times) of the spermine solution is added gradually increases, the fluorescence intensity of the fluorescent probe DCA-Tba gradually decreases, and when the spermine solution of 50. Mu. Mol/L is added, the fluorescence intensity is not changed any more, which indicates that the saturation state is reached. As shown in FIG. 7, the maximum UV absorption intensity of the fluorescent probe DCA-Tba gradually decreased when the concentration of spermine added was gradually increased (0 to 20 times), and the UV absorption intensity was not changed when 200. Mu. Mol/L of spermine solution was added, indicating that the saturation state was reached. In addition to aniline, other amines have similar effects.
Second, the detection limit for DCA-Tba recognition of spermine was calculated. Fluorescence intensities of not less than 11 replicates were tested with 10. Mu. Mol/L DCA-Tba solution according to the formula: sigma (X) i -X) 2 = (X 1 -X) 2 + (X 2 -X) 2 +……+ (X n -X) 2 Sum of squared differences (X i For each measurement of the fluorescence intensity value of the receptor itself, X is the average value of the fluorescence intensity, n is the number of tests, n.gtoreq.11), then according to the formula: s= [ Σ (X i -X) 2 /(n-1)] 0.5 The sensitivity S is obtained, and then according to a detection limit formula: detection limit=3s/K, where K is the slope of the selected straight line portion (note: straight line is a plot made from titration, abscissa is ion concentration, and ordinate is fluorescence intensity), and the detection limit is found to be 1.091×10 -5 mol/L (see FIG. 8). Obtaining y=ax+b (a is the slope of the selected straight line portion and B is the intercept) from the dot plot of the straight line made from the test result of the ultraviolet titration, and when y=0, obtaining the instantaneous detection limit, detecting limit=10 according to the formula -A/B (log spermine concentration on the abscissa and absorption intensity maximum-absorption on the ordinateThe ratio of the received intensity) to (absorption intensity maximum value-absorption intensity value) was determined to have a detection limit of 3.528 ×10 for ultraviolet light -6 mol/L (see figure 9), which shows that the probe can detect spermine with lower content in aqueous solution, has higher sensitivity and better practical application potential.
Again, the influence of pH on the detection of amine compounds is examined, and by taking spermine as an example, the fluorescence intensity of DCA-Tba under different pH conditions is shown in figure 10 (note: the ratio of fluorescence intensity at 600 and 700nm on the ordinate), and the probe DCA-Tba has better fluorescence intensity in the pH range of 5-11, indicating that the probe has better stability in weak acidity, neutrality and weak alkalinity. After the spermine solution is added into the probe, the ratio is increased, which shows that the fluorescence intensity at 600nm is gradually increased, and the pH is within the range of 5-11 by combining the remarkable degree of fluorescence change before and after recognition, the fluorescent probe DCA-Tba has remarkable recognition effect on spermine, and shows that the probe has wider pH application range.
Finally, the response time of the fluorescent probe for identifying the amine compound is explored, as shown in fig. 11, after the spermine solution is added into the solution containing the fluorescent probe, the change of the fluorescence intensity of the test solution at 600nm along with time is monitored by a fluorescence machine, obvious fluorescence signal enhancement is observed to be smooth within 2 hours, and a foundation is laid for the subsequent preparation of the fish freshness sensing label. In addition, we speculate that the mechanism by which the fluorescent probe DCA-Tba recognizes volatile amines is as follows:
nucleophilic substitution-elimination reaction of different volatile amine and probe DCA-Tba occurs, the conjugation length of the generated product is shortened compared with that of probe DCA-Tba, the push-pull electronic system is destroyed, fluorescence emission is moved from long wave emission to short wave direction, and absorption intensity is reduced.
3. Identification of volatile amines by the sensor tag in a simulated environment (cylindrical glass bottle 65, mm, 18, mm diameter)
The preparation process of the sensing label comprises the following steps: 3.95 mg DCA-Tba is weighed and dissolved in 10 mL DMSO, round filter paper with the diameter of 2cm is placed in the solution to be soaked overnight, and then the solution is taken out and dried, so that the fluorescent probe DCA-Tba sensing label is obtained, and the sensing label is green when observed with naked eyes and shows no fluorescence under ultraviolet light.
During the deterioration of fish meat, some metabolic volatile substances such as triethylamine, n-propylamine, diethylamine and the like are generated, and the freshness of the fish meat can be monitored by detecting the metabolic volatile substances. To verify whether the manufactured sensor tag is selective to volatile amine, we first place an aqueous solution containing 0.5% volatile amine in a vial, then place the sensor tag on top of the vial, and simulate whether the sensor tag responds to volatile amine in a fish spoilage environment.
Firstly, 2mL of volatile amine with the concentration of 50 mmol/L is taken and added into 3mL of distilled water to prepare 20 mmol/L volatile amine solution; respectively selecting 12 volatile amines such as ethylamine, diethylamine, triethylamine, n-propylamine and the like as experimental groups, and pure water as blank control groups. The 12 experimental groups and the blank control group are green when observed under natural light, and have no fluorescence under ultraviolet light. After the volatile amine is fumigated for 1 hour, the colors of the sensing labels of the 12 experimental groups are changed in different colors under natural light, pink or orange colors with different intensities are displayed under ultraviolet light (see figure 12), and the blank control group is unchanged. The sensing label has good colorimetric and fluorescent dual response to 12 volatile amines such as ethylamine, diethylamine, triethylamine, n-propylamine and the like, and has the potential of detecting the freshness of fish meat.
4. Preparation of sensing label standard colorimetric card
In order to obtain the relation between the color change of the sensing tag and the actual freshness level of the fish meat, the tag and the fish meat are stored together, the TVB-N content is measured by using the national standard regulation method of the people's republic of China, and a standard color chart is prepared for distinguishing the freshness level of the fish meat. The method comprises the steps of selecting salmon meat as an experimental object, peeling the salmon meat, dividing the salmon meat into a plurality of small fish meat blocks of 5-6 g, respectively placing the small fish meat blocks in a disposable round transparent plastic culture dish, placing a sensing tag in the headspace of a cover of the culture dish, fastening the cover, placing the cover in a refrigerator at the temperature of 4 ℃ for storage, detecting the TVB-N content of the salmon meat for 1 time every 24 hours, and collecting natural light pictures and fluorescent pictures of the sensing tag. The data obtained are shown in fig. 13. The TVB-N content of the fresh salmon meat is gradually increased from the initial 6.53+/-2.13 mg/100g overall, the TVB-N content reaches 15.46 +/-1.40 mg/100g on the 4 th day, then the TVB-N content starts to be rapidly increased, 30.18+/-0.53 mg/100g on the 8 th day, and the acceptable limit of the TVB-N is 30 mg/100 g. Thus, salmon meat is a threshold for storage deterioration that can be seen on day 8 of storage at 4 ℃. Under natural light, the color of the sensing label is changed from the original green to light pink and finally to dark pink; under the irradiation of 365 and nm ultraviolet light, when the sensing label is initially non-fluorescent, the sensing label turns into orange fluorescent, and finally turns into orange fluorescent.
According to the national standard GB/T18108-2019 (the general rule of fresh sea water fishes) of the people's republic of China, the highest limit of the TVB-N content in the sea water fishes is 30 mg/100 g. When the TVB-N value is less than or equal to 15 mg/100g, the sample is a high-grade product; when the TVB-N value is 15 mg/100g less than or equal to 30 mg/100g, the sample is qualified; when the TVB-N value is more than 30 mg/100g, the sample is a defective product.
According to the actual measured TVB-N value and the corresponding natural light color and ultraviolet light color photos of the sensing tag, we select the sensing tag with the TVB-N value of 6.53 mg/100g and 14.74 mg/100g to respectively show green and light green under natural light, and show no fluorescence and light pink fluorescence under ultraviolet light irradiation as the reference standard of the fresh part in the standard colorimetric card, and when the sensing tag displays one of the color states, we can judge that the sample is a fresh product (see the fresh area in FIG. 14). The sensing labels with TVB-N values of 15.46 mg/100g and 27.46 mg/100g are selected to respectively show light pink under natural light, and show medium-intensity orange fluorescent light under ultraviolet light irradiation, so that the sensing labels can be judged to be qualified products when the sensing labels show one of the color states as a reference standard of the qualified part in the standard color chart (see the qualified area in fig. 14). The sensor labels with TVB-N values of 30.18 mg/100g and 32 mg/100g are respectively pink under natural light, orange fluorescence is generated under ultraviolet light irradiation, and the orange fluorescence is used as a reference standard of the spoilage part in the standard colorimetric card, and when the sensor labels display one of the color states, the sample can be judged to be a spoilage product (see the spoilage area in fig. 14).
5. Practical application of sensing tag
The sensing label is used for actually monitoring the freshness of salmon. The change in color of the sensor tag with increasing storage time for salmon at 4 ℃ is shown in fig. 15. The sensing tag and newly purchased salmon are stored together, green is presented under natural light, and no fluorescence exists under ultraviolet light, and the sensing tag corresponds to the fresh part in the standard colorimetric card; when the storage time is 4 days, the natural light color of the sensing tag is light pink, and the sensing tag is medium-strength orange fluorescent light under ultraviolet light, and the sensing tag corresponds to the qualified part in the standard color chart, so that the fish meat is still a qualified product. When the storage time is further prolonged and reaches the 8 th day, the natural light color of the sensing label is bright pink, and the sensing label is orange fluorescent under ultraviolet light, which corresponds to the spoilage part in the standard color chart, so that the salmon meat is spoiled and is not edible.
In order to better improve the convenience of the sensing label, the sensing label is integrated with a standard colorimetric card, and an integrated label which can be used in commercialization is manufactured. As shown in fig. 16, the integrated tag takes a fish shape as a main body, and is composed of six square color cards with the same area and a circular sensing tag, wherein the six squares are a fresh color card, a qualified color card and a spoilage color card respectively, and the integrated tag is characterized in that: the color chart is divided into a natural light color comparison area and an ultraviolet light color comparison area, wherein the upper half area of the color chart is respectively a fresh natural light color comparison area, a qualified natural light color comparison area and a spoilage natural light color comparison area, and the lower half area of the color chart is respectively a fresh ultraviolet light color comparison area, a qualified ultraviolet light color comparison area and a spoilage ultraviolet light color comparison area. The circular area is the sensing label, and along with the extension of storage time, the color change of the sensing label of the circular area in the integrated label is observed, and the color of the colorimetric area is compared, so that the freshness of the fish meat can be judged.
Taking salmon as an example, the freshness of salmon is monitored using an integrated tag. Placing salmon purchased in a supermarket into a cutlery box, sealing with a plastic film, punching a round hole on the film, aligning a sensing label of an integrated label with the round hole, attaching the sensing label on the film, and recording the change of the label color along with the storage time at room temperature. As can be seen from FIG. 17, the color of the sensor tag corresponds to the color of the fresh portion of the color chart, and the TVB-N value is 6.27 mg/100g, which proves that the fish is in a fresh state. After 18 hours of standing at room temperature for h hours, the color of the sensing label corresponds to the color of the qualified area in the colorimetric card, and the TVB-N value is 16.8 mg/100g, so that the fish meat is proved to be in the qualified range. After 32 h is placed at room temperature, the color of the sensing tag corresponds to the spoilage part in the colorimetric card, and the TVB-N value is 31.36 mg/100g, which indicates that the salmon meat actually exceeds the national standard and cannot be eaten.
In summary, no matter in the application of simulating environment and real fish meat, the sensing tag disclosed by the invention can detect the freshness of fish meat in a non-contact, nondestructive, colorimetric and fluorescent dual-channel manner, is more accurate and reliable in qualitative analysis, can provide real-time effective freshness information for manufacturers, retailers and consumers, and has a better practical application value.
Claims (6)
1. The utility model provides a volatile amine fluorescent probe and binary channels instruction card's that preparation is in flesh of fish freshness detection application, characterized by: the structural formula of the probe is as follows:。
2. the application of the volatile amine fluorescent probe and the dual-channel indicator card prepared by the same in fish freshness detection is characterized in that: the specific synthesis steps are as follows: ethanol is taken as a solvent, benzopyran derivative and 2-thiobarbituric acid are added according to the mol ratio of 1 (1-1.5), and the benzopyran derivative is 6- (diethylamino) -1, 2-dihydro cyclopentane [ b ]]Benzopyran-3-carboxaldehydeThen adding piperidine according to the mass ratio of benzopyran derivative to piperidine of 100:1, heating, refluxing and stirring for 2-4 hours, cooling to room temperature, filtering and collecting solid, washing with ethanol for 3 times to obtain fluorescent probe DCA-Tba->。
3. The fluorescent probe for volatile amine and the dual-channel indicator card prepared by the fluorescent probe for volatile amine, as claimed in claim 1, wherein the indicator card takes a fish shape as a main body, and consists of six square color cards with the same area and a circular sensing tag, and the six squares are respectively a fresh color card, a qualified color card and a spoilage color card, and the fluorescent probe for volatile amine is characterized in that: the color chart is divided into a natural light color comparison area and an ultraviolet light color comparison area, wherein the upper half area of the color chart is respectively a fresh natural light color comparison area, a qualified natural light color comparison area and a spoilage natural light color comparison area, and the lower half area of the color chart is respectively a fresh ultraviolet light color comparison area, a qualified ultraviolet light color comparison area and a spoilage ultraviolet light color comparison area; the specific preparation process of the sensing label comprises the following steps: adding 10 mL dimethyl sulfoxide (DMSO) solution into 10 mg fluorescent probe, soaking cut round filter paper sheet in the probe solution, taking out and drying after overnight, and obtaining the sensing tag for monitoring fish freshness.
4. The volatile amine fluorescent probe and the dual-channel indicator card prepared by the same according to claim 3, wherein the dual-channel indicator card is characterized in that: the color phase corresponding to the natural light color comparison area of the fresh product is green, and the color phase corresponding to the ultraviolet light color comparison area of the fresh product is non-fluorescent; the hue corresponding to the natural light colorimetric region of the qualified product is light pink, and the hue corresponding to the ultraviolet colorimetric region of the qualified product is fluorescent orange pink; the color phase corresponding to the natural light color comparison area of the unqualified product is dark pink, and the color phase corresponding to the ultraviolet light color comparison area of the unqualified product is orange fluorescence.
5. A use of the volatile amine fluorescent probe according to claim 3 and a dual channel indicator card prepared therefrom for determining freshness of fish meat.
6. The application of the volatile amine fluorescent probe and the dual-channel indicator card prepared by the same in judging the freshness of fish meat, which is characterized in that: aligning a sensing tag in the integrated tag to a packaging opening, and comparing the sensing tag with a standard color chart according to the color change of the sensing tag without directly contacting with the fish meat, monitoring the freshness of the fish meat in real time, and judging the grade of the fish meat; under visible light, the color of the sensing tag is green to indicate that the fish meat is in a fresh grade, the color of the sensing tag is light pink to indicate that the fish meat is in a qualified grade, and the color of the sensing tag is dark pink to indicate that the fish meat is in a spoilage grade; under the irradiation of 365 and nm ultraviolet light, the fish meat is in a fresh grade when the color of the sensing label is non-fluorescent, the fish meat is in a qualified grade when the color of the sensing label is orange pink fluorescent with medium intensity, and the fish meat is in a spoilage grade when the color of the sensing label is orange fluorescent.
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